Tracing the sources of strontium in karst groundwater in Chongqing, China: a combined hydrogeochemical approach and strontium isotope

Groundwater quality in karst regions is largely controlled by natural processes and anthropogenic activities. Over the past 10?years, dissolved Sr and its radiogenic isotope, ⁸⁷Sr/⁸⁶Sr, were widely used to trace the sources of solutes in groundwater. However, there is little research about hydrogeochemistry and Sr isotopic compositions of the karst groundwater in Chongqing karst area. In this paper, thirty-five representative karst groundwater samples were collected from different aquifers (limestone and dolomite) and various land use types. Hydrochemical types of karst groundwater in Chongqing were mainly of the Ca-HCO₃ type or Ca(Mg)-HCO₃ type. The dissolved Sr concentrations of the studied groundwater ranged from 0.57 to 15.06???mmol/L, and the ⁸⁷Sr/⁸⁶Sr varied from 0.70751 to 0.71627. The groundwater samples from different aquifers and land use types showed distinctive dissolved Sr concentrations and ⁸⁷Sr/⁸⁶Sr. The very positive relationship between Ca/Sr and Mg/Sr in dolomite and limestone aquifers suggests that Ca, Mg and Sr element come mainly from the release of carbonate rock under the groundwater?Crock?CCO₂ gas interaction. According to the ⁸⁷Sr/⁸⁶Sr ratio, the Sr element in karst groundwater in Chongqing was controlled by the weathering of limestone, dolomite and silicate rock (allogenic water in a non-karst area). The relationship ⁸⁷Sr/⁸⁶Sr versus Sr²⁺/[K⁺?+?Na⁺] shows that the anthropogenic inputs also obviously contribute to the Sr contents. The research results show that the karst groundwater in Chongqing is facing serious crisis of water quality, and needs to be protected further.     

氮同位素技术的应用:土壤有机氮作为地下水硝酸盐污染源的条件分析

在土壤排水良好、氧化的地下水环境中,地下水的氮同位素组成反映了源的特征。当地下水硝酸盐的δ15N值在+4‰～+9‰范围内时,这个值域指示地下水硝酸盐污染源是土壤有机氮或化肥与粪便的混合。通过分析对比前人研究资料,地下水中硝酸盐是否来自土壤有机氮的转化,其前提条件是研究区土壤有机氮是否丰富,特别是包气带中是否积累了大量有机氮转化的NO3-,并以石家庄市地下水硝酸盐污染为例,说明了这种条件分析在氮同位素技术应用时的重要性。通过包气带岩性、有机质和NO3-含量分析、施肥区与未施肥区灌水试验对比,土壤有机氮不是石家庄市地下水NO3-的一个主要污染源。当地下水硝酸盐低浓度时(1991),85.7%的样品NO3-的δ15N值在+6.1‰～+8.4‰范围内,指示污染源主要为化肥与粪便的混合,而当现今的高浓度时,样品硝酸盐的δ15N均值(+9.9‰±4.4‰)大于+8‰和超过半数(65%)样品的δ15N值大于+8‰,指示污染源主要是粪便或含粪便的污水。     

Tracking sources of groundwater nitrate contamination using nitrogen and oxygen stable isotopes at Beijing area,China

The identification of sources and behavior of contaminants is important to control and manage groundwater quality of aquifer systems in urban areas. In this study, hydrogeochemistry of major constituents and stable isotope ratios of nitrate in groundwater were determined to identify contamination sources and transformation processes occurring in soils and deeper groundwater of Beijing with intense human activities. The nitrogen and oxygen isotopic compositions of nitrate in pore water extracts from groundwater samples indicate at least three potential sources of nitrate in groundwaters at Beijing. Stable isotope analyses from this study site, which has atmospheric, chemical fertilizer and human waste nitrate sources, provide a tool to distinguish nitrate sources in a confined aquifer where concentrations alone do not. These data indicate that the most common sources of high nitrate concentrations in groundwater at Beijing are wastewater and denitrification process occurred specially in the Central area. NO₃–N and cation and anion concentrations (Ca²⁺, Mg²⁺ Cl^? and SO ₄ ² ) showed strong correlations indicating that they originated from the same sources. This study demonstrates that a thorough evaluation of hydrodynamic and hydrochemical parameters with dual isotopes of NO₃ ^? constitutes an effective approach for identifying sources and transformation processes of NO₃ ^? in deeper groundwater systems.     

西南喀斯特地区水体硝态氮时空分布特征及其来源解析

由于人类活动影响,水体硝态氮污染已经成为世界范围内的环境问题。硝态氮污染不仅会造成水体富营养化,长期摄入过量硝酸盐还会严重威胁人体健康,控制并解决水体硝态氮污染是我国经济社会发展过程中亟待解决的重要环境问题。我国西南喀斯特地区是世界上面积最大、发育最典型和人地矛盾尖锐的岩溶连续分布带,具有十分脆弱且高度敏感的生态系统。与非喀斯特地区相比,这里水体硝态氮污染情况更为复杂和严重。因此,明确西南喀斯特地区内硝态氮的时空分布特征并对其来源进行解析是有效治理的前提。本研究梳理了近几十年来西南喀斯特地区水体硝态氮的现代监测结果,探讨了水体硝态氮时空分布特征、来源及受控机制等问题,发现:(1)区域内地表水硝态氮平均检出质量浓度不高,地下水检出质量浓度波动范围较大;(2)近几十年来,地表水硝态氮质量浓度整体呈现小幅增长趋势,而地下水检出质量浓度随时间的变化存在地域差异;(3)降水的稀释和冲携作用对区域内硝态氮质量浓度及分布的影响不容忽视,而人类活动导致的土地利用变化带来的影响可能成为未来的主控因素;(4)区域内水体硝态氮主要来源于铵态化肥、土壤有机氮、粪肥及污水,硝化作用是主要的转化过程。研究结果将为进一步认识喀斯特地区氮循环过程及促进地区可持续发展提供理论基础。     

Assessment of groundwater chemistry in a coastal region (Kunsan, Korea) having complex contaminant sources: a stoichiometric approach

Groundwater chemistry in a coastal region (Kunsan, Korea) having complex contaminant sources was investigated. Water analysis data for 197 groundwater samples collected from the uniformly distributed sixty-six wells were used. Chemical analysis results indicate that groundwaters show wide concentration ranges in major inorganic ions, reflecting complex hydrochemical processes. Due to the complexity of groundwater chemistry, the samples were classified into four groups based on Cl and NO₃ concentrations and the processes controlling water chemistry were evaluated based on the reaction stoichiometry. The results explained the importance of mineral weathering, anthropogenic activities (nitrification and oxidation of organic matters), and Cl-salt inputs (seawater, deicer, NaCl, etc.) on groundwater chemistry. It was revealed that mineral dissolution is the major process controlling the water chemistry of the low Cl and NO₃ group (Group 1). Groundwaters high in NO₃ (Groups 2 and 4) are acidic in nature, and their chemistry is largely influenced by nitrification, oxidation of organic matters and mineral dissolution. In the case of chloride rich waters (Group 3), groundwater chemistry is highly influenced by mineral weathering and seawater intrusion associated with cation-exchange reactions.     

Detection of nitrate sources in urban groundwater by isotopic and chemical indicators,Hangzhou City,China

The sources of nitrate in the shallow groundwater at urban area, Hangzhou City, China were investigated using chemical and isotopic techniques. Groundwater electric conductivity was high in the study area and ranged from 369–1,544 S/cm. Most of the groundwater was weakly alkaline and the groundwater chemistry was seriously influenced by land use in the city. There was a high frequency of groundwater (43% of total) with nitrate above World Heath Organizations standards of 10 mg NO₃/L. The different land-use areas had different nitrate concentrations (0.04–34.41 mgN/L) and ¹⁵N _NO3 values (7.8~35.5). Domestic wastewater was the major nitrate source of shallow groundwater in the urban area, and the point source (septic tank) still existed in residential settings. At agricultural settings manure was the major NO₃ sources. High ¹⁵N _NO3 value (>20) and temporal variations of the ¹⁵N _NO3 value suggested that in residential areas it probably resulted from denitrification.     

Characteristics of groundwater and urban emergency water sources optimazation in Luoyang,China

The construction of emergency water sources is the material basis for ensuring urban water safety, and it is also an inherent requirement for maintaining social stability and development. The hydrogeological characteristics of groundwater in Luoyang City from the aspects of the division of groundwater aquifer groups, water yield property and groundwater dynamics were described in this paper. Two emergency water sources were selected on basis of comprehensively considering groundwater resources and ecological environmental effects, groundwater quality and exploitation technology, etc. Then it further analysed the aquifer types, water yield properties and groundwater recharge, runoff and discharge conditions of the two emergency water sources, and evaluate the groundwater resources quantity of the water sources. The results are that the shallow underground aquifer in Luoyang City is thick, coarse, and stable in lithology and thickness. The two water sources enjoy good exploitation potential and can be used as backup water sources to supply water in the event of a water source crisis.     

Tracing stable isotope values from meteoric water to groundwater in the southwestern part of the Chad basin

The southwestern Chad basin is a semi-arid region with annual rainfall that is generally less than 500 mm and over 2,000 mm of evapotranspiration. Surface water in rivers is seasonal, and therefore groundwater is the perennial source of water supply for domestic and other purposes. Stable isotope has been measured for rainwater, surface water and groundwater samples in this region. The stable isotope data have been used to understand the inter-relationships between the rainwater, surface water, shallow and deep groundwater of this region. This is being used in a qualitative sense to demonstrate present day recharge to the groundwater. Stable isotope in rainwater for the region has an average value of –4‰ δ¹⁸O and –20‰ δ²H. Surface water samples from rivers and Lake Chad fall on the evaporation line of this average value. The Upper Zone aquifer water samples show stable isotope signal with a wide range of values indicating the complex character of the aquifer Zone with three distinguishable units. The wide range of values is attributable to waters from individual unit and/or mixture of waters of different units. The Middle and Lower aquifers Zones’ waters show similar stable isotopes values, probably indicating similarity in timing and/or mechanism of recharge. These are palaeowaters probably recharged under a climate that is different from today. The Upper Zone aquifer is presently being recharged as some of its waters show stable isotope compositions similar to those of average rainfall waters of the region.     

Seasonal and spatial variations in water chemistry and nitrate sources in six major Korean rivers

Seasonal and spatial variations in water chemistry and contaminant sources were investigated in six major rivers in South Korea that vary widely in drainage area and length. The dissolved-load content of the rivers varied seasonally, and some dissolved ions such as Cl^? and NO₃ ^? showed large spatial differences in all of the rivers. The water type changed from Ca–HCO₃ in the upper reaches to Na–Cl–NO₃ in the lower reaches, indicating anthropogenic contamination in the lower reaches. Compared with two relatively pristine rivers (the Sumjin and Mankyung rivers), the other four rivers, which flow through agricultural and urban areas, registered much higher Cl^? and NO₃ ^? concentrations. Statistical analysis showed that seasonal and spatial variations in water chemistry occurred in all the rivers. The nitrogen and oxygen isotopes of dissolved nitrate indicated that the rivers flowing through urban and agricultural areas were significantly affected by manure, sewage, or both.     

Rare earth geochemistry in the dissolved, suspended and sedimentary loads in karstic rivers, Southwest China

The watershed in the central Guizhou Province (Guizhou Province is called simply Qian) (CQW) is a karstic area. Rare earth elements (REEs) of dissolved loads, suspended particulate material (SPM) and sediments of riverbed are first synthetically reported to investigate REE geochemistry in the three phases in karstic watershed during the high-flow season. Results show that the low dissolved REE concentrations in the CQW are attributed to these rivers draining carbonate rocks. The dissolved REE have significant negative Eu anomaly and coexistence of middle and light REE (MREE??PAAS-normalized La _N /Sm _N and Gd _N /Yb _N ; LREE??PAAS-normalized La _N /Yb _N )-enrichment, which are due to the dissolution of impure Triassic carbonates. REE concentrations in most of SPM exceed that of sediments in the CQW and the average continental crust (UCC). The SPM and the sediments show some common features: positive Eu, Ce anomalies, and MREE enrichment. The controls on the patterns seem to be from weathering profiles: the oxidation state, the REE-bearing secondary minerals (cerianite, potassium feldspar and plagioclase), which are also supported by the evidence of Y/Ho fractionations in the three phases.     

Mixing of shallow and deep groundwater as indicated by the chemistry and age of karstic springs

Large karstic springs in east-central Florida, USA were studied using multi-tracer and geochemical modeling techniques to better understand groundwater flow paths and mixing of shallow and deep groundwater. Spring water types included Ca–HCO₃ (six), Na–Cl (four), and mixed (one). The evolution of water chemistry for Ca–HCO₃ spring waters was modeled by reactions of rainwater with soil organic matter, calcite, and dolomite under oxic conditions. The Na–Cl and mixed-type springs were modeled by reactions of either rainwater or Upper Floridan aquifer water with soil organic matter, calcite, and dolomite under oxic conditions and mixed with varying proportions of saline Lower Floridan aquifer water, which represented 4–53% of the total spring discharge. Multiple-tracer data—chlorofluorocarbon CFC-113, tritium (³H), helium-3 (³He_trit), sulfur hexafluoride (SF₆)—for four Ca–HCO₃ spring waters were consistent with binary mixing curves representing water recharged during 1980 or 1990 mixing with an older (recharged before 1940) tracer-free component. Young-water mixing fractions ranged from 0.3 to 0.7. Tracer concentration data for two Na–Cl spring waters appear to be consistent with binary mixtures of 1990 water with older water recharged in 1965 or 1975. Nitrate-N concentrations are inversely related to apparent ages of spring waters, which indicated that elevated nitrate-N concentrations were likely contributed from recent recharge.An erratum to this article can be found at     

Nitrogen and oxygen isotopic compositions of water-soluble nitrate in Taihu Lake water system, China: implication for nitrate sources and biogeochemical process

The stable isotope nitrogen-15 (¹⁵N) is a robust indicator of nitrogen (N) source, and the joint use of δ¹⁵N and δ¹⁸O–NO₃ ^? values can provide more useful information about nitrate source discrimination and N cycle process. The δ¹⁵N and δ¹⁸O–NO₃ ^? values, as well as major ion tracers, from Taihu Lake in east China were investigated to identify the primary nitrate sources and assess nitrate biogeochemical process in the present study. The results show that the nitrate concentration in West Taihu Lake (WTL) was generally higher than those in East Taihu Lake (ETL) and its upstream inflow rivers. The NO₃ ^?/Cl^? value combined with mapping of δ¹⁵N–NO₃ ^? and NO₃ ^? concentration suggest that the mixing process should play a major effect in WTL, and denitrification was the dominant N transformation process in WTL. A linear relationship of close to ~1: 2 was observed between δ¹⁵N–NO₃ ^? and δ¹⁸O–NO₃ ^? values in WTL, confirming the occurrence of denitrification in WTL. The δ¹⁵N–NO₃ ^? data imply that sewage and manure were the principal nitrate sources in WTL and its feeder rivers, while the nitrate in ETL might derive from soil organic nitrogen and atmospheric deposition. The δ¹⁸O–NO₃ ^? data indicate most of nitrate from microbial nitrification of organic nitrogen matter possibly make a significant contribution to the lake.     

Mixing of shallow and deep groundwater as indicated by the chemistry and age of karstic springs

Large karstic springs in east-central Florida, USA were studied using multi-tracer and geochemical modeling techniques to better understand groundwater flow paths and mixing of shallow and deep groundwater. Spring water types included Ca–HCO₃ (six), Na–Cl (four), and mixed (one). The evolution of water chemistry for Ca–HCO₃ spring waters was modeled by reactions of rainwater with soil organic matter, calcite, and dolomite under oxic conditions. The Na–Cl and mixed-type springs were modeled by reactions of either rainwater or Upper Floridan aquifer water with soil organic matter, calcite, and dolomite under oxic conditions and mixed with varying proportions of saline Lower Floridan aquifer water, which represented 4–53% of the total spring discharge. Multiple-tracer data—chlorofluorocarbon CFC-113, tritium (³H), helium-3 (³He_trit), sulfur hexafluoride (SF₆)—for four Ca–HCO₃ spring waters were consistent with binary mixing curves representing water recharged during 1980 or 1990 mixing with an older (recharged before 1940) tracer-free component. Young-water mixing fractions ranged from 0.3 to 0.7. Tracer concentration data for two Na–Cl spring waters appear to be consistent with binary mixtures of 1990 water with older water recharged in 1965 or 1975. Nitrate-N concentrations are inversely related to apparent ages of spring waters, which indicated that elevated nitrate-N concentrations were likely contributed from recent recharge.The online version of the original article can be found at     

A multi-analysis remote-sensing approach for mapping groundwater resources in the karstic Meo Vac Valley, Vietnam

Remote sensing data can be integrated with analyses of topography, structural geology, hydrogeology and geophysics. The integration gives premises for the delineation of zones of potential groundwater resources in strongly fractured and karstified deep aquifers in the uplifted Meo Vac Highland, northern Vietnam. Remote sensing analysis outlines geological faults with hydrogeological significance. These faults are combined with a derived lineament density map, interpreted analysis of surface flow direction and existing hydrogeological data, resulting in indications of groundwater flow direction. An analysis of the SPOT 5 band ratio 4/1, together with indications of surface-flow direction in low terrains, results in a determination of underground cavern passages. The delineated zones of potential groundwater resources are verified by detailed hydrogeological field surveys and geophysical measurements. Remote sensing analysis is shown to effectively contribute to the investigation of groundwater resources for a hydrogeologically complex area.     

Surface water chemistry and nitrate pollution in Shimabara,Nagasaki, Japan

Groundwater is a finite resource that is threatened by pollution all over the world. Shimabara City, Nagasaki, Japan, uses groundwater for its main water supply. During recent years, the city has experienced severe nitrate pollution in its groundwater. For better understanding of origin and impact of the pollution, chemical effects and surface–groundwater interactions need to be examined. For this purpose, we developed a methodology that builds on joint geochemical analyses and advanced statistical treatment. Water samples were collected at 42 sampling points in Shimabara including a part of Unzen City. Spatial distribution of water chemistry constituents was assessed by describing Stiff and Piper diagrams using major ions concentrations. The nitrate (NO₃?+?NO₂–N) concentration in 45% of water samples exceeded permissible Japanese drinking level of 10 mg L^??1. Most of the samples showed Ca–HCO₃ or Ca–(NO₃?+?SO₄) water types. Some samples were classified into characteristic water types such as Na–Cl, (Na?+?K)–HCO₃, (Na?+?K)–(SO₄?+?NO₃), and Ca–Cl. Thus, results indicated salt water intrusion from the sea and anthropogenic pollution. At the upstream of Nishi River, although water chemistry was characterized as Ca–HCO₃, ion concentrations were higher than those of other rivers. This is probably an effect of disinfection in livestock farming using slaked lime. Positive correlation between NO₃^? and SO₄^2?, Mg²⁺, Ca²⁺, Na⁺, K⁺, and Cl^? (r?=?0.32–0.64) is evidence that nitrate pollution sources are chemical fertilizers and livestock waste. Principal component analysis showed that chemistry of water samples can be explained by three main components (PCs). PC1 depicts general ion concentration. PC2 and PC3 share influence from chemical fertilizer and livestock waste. Cluster analyses grouped water samples into four main clusters. One of these is the general river chemistry mainly affected by PC1. The others reflect anthropogenic activities and are identified by the combination of the three PCs.     

Sources of nitrate contamination and age of water in large karstic springs of Florida

In response to concerns about the steady increase in nitrate concentrations over the past several decades in many of Floridas first magnitude spring waters (discharge 2.8 m³/s), multiple isotopic and other chemical tracers were analyzed in water samples from 12 large springs to assess sources and timescales of nitrate contamination. Nitrate-N concentrations in spring waters ranged from 0.50 to 4.2 mg/L, and ¹⁵N values of nitrate in spring waters ranged from 2.6 to 7.9 per mil. Most ¹⁵N values were below 6 per mil indicating that inorganic fertilizers were the dominant source of nitrogen in these waters. Apparent ages of groundwater discharging from springs ranged from 5 to about 35 years, based on multi-tracer analyses (CFC-12, CFC-113, SF₆, ³H/³He) and a piston flow assumption; however, apparent tracer ages generally were not concordant. The most reliable spring-water ages appear to be based on tritium and ³He data, because concentrations of CFCs and SF₆ in several spring waters were much higher than would be expected from equilibration with modern atmospheric concentrations. Data for all tracers were most consistent with output curves for exponential and binary mixing models that represent mixtures of water in the Upper Floridan aquifer recharged since the early 1960s. Given that groundwater transit times are on the order of decades and are related to the prolonged input of nitrogen from multiple sources to the aquifer, nitrate could persist in groundwater that flows toward springs for several decades due to slow transport of solutes through the aquifer matrix.     

Compilation simulation of surface water and groundwater resources using the SWAT-MODFLOW model for a karstic basin in Iran

Modeling of karstic basins can provide a better understanding of the interactions between surface water and groundwater, a more accurate estimation of infiltrated water amount, and a more reliable water balance calculation. In this study, the hydrological simulation of a karstic basin in a semiarid region in Iran was performed in three different stages. In the first stage, the original SWAT model was used to simulate surface-water flow. Then, the SWAT-MODFLOW conjunctive model was implemented according to the groundwater characteristics of the study area. Finally, due to the karstic characteristics of the region and using the CrackFlow (CF) package, the SWAT-MODFLOW-CF conjunctive model was developed to improve the simulation results. The coefficient of determination (R²) and the Nash-Sutcliffe efficiency coefficient (NSE) as error evaluation criteria were calculated for the models, and their average values were 0.63 and 0.57 for SWAT, 0.68 and 0.61 for SWAT-MODFLOW, 0.73 and 0.7 for SWAT-MODFLOW-CF, respectively. Moreover, the mean absolute error (MAE) and root mean squared error (RMSE) of the calibration for groundwater simulation using the SWAT-MODFLOW model were 1.23 and 1.77 m, respectively. These values were 1.01 and 1.33 m after the calibration of the SWAT-MODFLOW-CF model. After modifying the CF code and keeping the seams and cracks open in both dry and wet conditions, the amount of infiltrated water increased and the aquifer water level rose. Therefore, the SWAT-MODFLOW-CF conjunctive model can be proposed for use in karstic areas containing a considerable amount of both surface water and groundwater resources.